JP4790381B2 - Polymer light-emitting material, organic electroluminescence element, and display device - Google Patents
Polymer light-emitting material, organic electroluminescence element, and display device Download PDFInfo
- Publication number
- JP4790381B2 JP4790381B2 JP2005328724A JP2005328724A JP4790381B2 JP 4790381 B2 JP4790381 B2 JP 4790381B2 JP 2005328724 A JP2005328724 A JP 2005328724A JP 2005328724 A JP2005328724 A JP 2005328724A JP 4790381 B2 JP4790381 B2 JP 4790381B2
- Authority
- JP
- Japan
- Prior art keywords
- represented
- group
- polymer
- organic
- polymerizable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims description 76
- 239000000463 material Substances 0.000 title claims description 68
- 238000005401 electroluminescence Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 82
- 125000001424 substituent group Chemical group 0.000 claims description 51
- 229910052741 iridium Inorganic materials 0.000 claims description 37
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 37
- 230000005525 hole transport Effects 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229920000620 organic polymer Polymers 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 63
- 238000000034 method Methods 0.000 description 36
- 125000000524 functional group Chemical group 0.000 description 30
- 229920001577 copolymer Polymers 0.000 description 17
- 125000005843 halogen group Chemical group 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 125000003710 aryl alkyl group Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000001072 heteroaryl group Chemical group 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 0 C*(C)Cc1cccc(N(C2)c3ccc(C(CCc(cc4)ccc4-[n]4c(cccc5)c5c5c4cccc5)c(cc4)ccc4-[n]4c(ccc(C=C)c5)c5c5ccccc45)cc3)c1C2=CC=CC* Chemical compound C*(C)Cc1cccc(N(C2)c3ccc(C(CCc(cc4)ccc4-[n]4c(cccc5)c5c5c4cccc5)c(cc4)ccc4-[n]4c(ccc(C=C)c5)c5c5ccccc45)cc3)c1C2=CC=CC* 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000000872 buffer Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- -1 mesityl group Chemical group 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 150000001923 cyclic compounds Chemical class 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 150000002503 iridium Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- 229940093475 2-ethoxyethanol Drugs 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000006617 triphenylamine group Chemical group 0.000 description 2
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical class C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- GZEXHGDBYMTBCP-UHFFFAOYSA-N 2-carbamoyloxyethyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCOC(N)=O GZEXHGDBYMTBCP-UHFFFAOYSA-N 0.000 description 1
- UPSWHSOSMRAWEH-UHFFFAOYSA-N 2-n,3-n,4-n-tris(3-methylphenyl)-1-n,1-n,2-n,3-n,4-n-pentakis-phenylbenzene-1,2,3,4-tetramine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C(=C(N(C=3C=CC=CC=3)C=3C=C(C)C=CC=3)C(N(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 UPSWHSOSMRAWEH-UHFFFAOYSA-N 0.000 description 1
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 1
- 229910017073 AlLi Inorganic materials 0.000 description 1
- 241001136782 Alca Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UAOODKMNHMYSBK-UHFFFAOYSA-N C=Cc(cc1)cc(c2ccccc22)c1[n]2-c(cc1)ccc1-c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2 Chemical compound C=Cc(cc1)cc(c2ccccc22)c1[n]2-c(cc1)ccc1-c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2 UAOODKMNHMYSBK-UHFFFAOYSA-N 0.000 description 1
- JUDADOUJZHIVTB-UHFFFAOYSA-N C=Cc(cc1)cc(c2ccccc22)c1[n]2-c(cc1)ccc1-c(cc1)ccc1N1C2=CCCC=C2c2c1cccc2 Chemical compound C=Cc(cc1)cc(c2ccccc22)c1[n]2-c(cc1)ccc1-c(cc1)ccc1N1C2=CCCC=C2c2c1cccc2 JUDADOUJZHIVTB-UHFFFAOYSA-N 0.000 description 1
- SMVXHONPZPRFQQ-UHFFFAOYSA-N CC(C)(C)c(cc1)ccc1-c1nnc(C2C=CC(c3ccc(C=C)cc3)=CC2)[o]1 Chemical compound CC(C)(C)c(cc1)ccc1-c1nnc(C2C=CC(c3ccc(C=C)cc3)=CC2)[o]1 SMVXHONPZPRFQQ-UHFFFAOYSA-N 0.000 description 1
- MMDJYEGZPXNCSU-ABLWVSNPSA-N CC1O[C@H](C)[O]=C(CCc2ccc(C=C)cc2)C1 Chemical compound CC1O[C@H](C)[O]=C(CCc2ccc(C=C)cc2)C1 MMDJYEGZPXNCSU-ABLWVSNPSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 239000007877 V-601 Substances 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VNJGVUDVNNPPAG-UHFFFAOYSA-K aluminum;quinolin-2-olate Chemical compound [Al+3].C1=CC=CC2=NC([O-])=CC=C21.C1=CC=CC2=NC([O-])=CC=C21.C1=CC=CC2=NC([O-])=CC=C21 VNJGVUDVNNPPAG-UHFFFAOYSA-K 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004305 biphenyl Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- AHLBNYSZXLDEJQ-FWEHEUNISA-N orlistat Chemical compound CCCCCCCCCCC[C@H](OC(=O)[C@H](CC(C)C)NC=O)C[C@@H]1OC(=O)[C@H]1CCCCCC AHLBNYSZXLDEJQ-FWEHEUNISA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- XYKIUTSFQGXHOW-UHFFFAOYSA-N propan-2-one;toluene Chemical compound CC(C)=O.CC1=CC=CC=C1 XYKIUTSFQGXHOW-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000004322 quinolinols Chemical class 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Landscapes
- Electroluminescent Light Sources (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、高分子発光材料および有機エレクトロルミネッセンス素子に関する。より詳しくは、本発明は、高い純度の青色光が高い発光効率で得られる高分子発光材料、および製造工程が簡略化され、大面積化が実現できるとともに、耐久性に優れた有機エレクトロルミネッセンス素子に関する。 The present invention relates to a polymer light emitting material and an organic electroluminescence device. More specifically, the present invention relates to a polymer light-emitting material capable of obtaining high-purity blue light with high light emission efficiency, and an organic electroluminescence device that has a simplified manufacturing process, can achieve a large area, and has excellent durability. About.
近年、有機エレクトロルミネッセンス素子（本明細書において、「有機ＥＬ素子」ともいう。）に用いる材料開発が活発に行われている。たとえば、フルカラー表示を実現するためには、光の３原色（ＲＧＢ）（赤色、緑色および青色）の各単色光を発光する材料が必要であるが、これらに関しては、高い発光効率とともに、高い純度を示す材料が求められている。 In recent years, materials for use in organic electroluminescent elements (also referred to as “organic EL elements” in this specification) have been actively developed. For example, in order to realize full color display, materials that emit light of each of the three primary colors (RGB) (red, green, and blue) of light are necessary. There is a need for materials that exhibit
青色の発光を示す錯体としては、最近、カルバゾール誘導体を有する配位子を有する金属錯体が開示されている。（特許文献１）
しかしながら、該錯体ではいまだ発光効率、寿命などの点で不充分である。さらに、発光層を形成する際に、上記錯体のような低分子化合物では、真空蒸着法が用いられるが、この方法で得られる発光層の膜厚は不均一になりやすい。
As a complex exhibiting blue light emission, a metal complex having a ligand having a carbazole derivative has been recently disclosed. (Patent Document 1)
However, this complex is still insufficient in terms of luminous efficiency, lifetime and the like. Furthermore, when forming the light emitting layer, a vacuum deposition method is used for a low molecular compound such as the above complex, but the film thickness of the light emitting layer obtained by this method tends to be uneven.
同特許文献１には、当該金属錯体を高分子中に分散させたポリマー組成物、すなわちドープ型発光材料も記載されている。当該ポリマー組成物で発光層を形成する場合は塗布法も利用できると記載がある。しかしながら、ドープ型発光材料は熱安定性に劣り、相分離または偏析を起こしやすい。該特許文献１でも該ポリマー組成物を用いた発光層の形成については具体的記載はない。
本発明の目的は、高い純度の青色光が高い発光効率で得られる高分子発光材料を提供することにある。また、本発明の別の目的は、製造工程が簡略化され、大面積化が実現できるとともに、耐久性に優れた有機ＥＬ素子および表示装置を提供することにある。 An object of the present invention is to provide a polymer light-emitting material from which high-purity blue light can be obtained with high luminous efficiency. Another object of the present invention is to provide an organic EL element and a display device that have a simplified manufacturing process, can achieve a large area, and are excellent in durability.
本発明者らは、上記課題を解決すべく鋭意研究した結果、特定のイリジウム錯体から導かれる構造単位を含む重合体からなる高分子発光材料により、高い純度の青色光が高い発光効率で得られることを見出し、本発明を完成するに至った。
すなわち、本発明は以下のとおりに要約される。
As a result of diligent research to solve the above problems, the present inventors can obtain high-purity blue light with high luminous efficiency by a polymer light-emitting material comprising a polymer containing a structural unit derived from a specific iridium complex. As a result, the present invention has been completed.
That is, the present invention is summarized as follows.
［１］ 下記一般式（１）〜（６）のいずれかで表されるイリジウム錯体から導かれる構造単位を含む重合体からなることを特徴とする高分子発光材料。 [1] A polymer light emitting material comprising a polymer including a structural unit derived from an iridium complex represented by any one of the following general formulas (1) to (6).
（式中、Ｘ1〜Ｘ7はそれぞれ独立に水素原子、ハロゲン原子、シアノ基、ニトロ基、炭素
数１〜１０のアルコキシ基、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アルキル基、炭素数６〜２１個のアリール基、炭素数２〜２０のヘテロアリール基もしくは炭素数７〜２１のアラルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アリール基、ハロゲン置換ヘテロアリール基もしくはハロゲン置換アラルキル基を表す。また、環Ａは窒素原子を含む環状化合物から誘導される２価の置換基であり、該窒素原子はイリジウムに結合しており、Ｘ1〜Ｘ7で定義される基と同様の置換基を有していてもよい。Ｌは、重合性官能基を有する、１価アニオンの２座配位子を表す。）
(Wherein, X 1 to X 7 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 10 carbon atoms, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or A halogen-substituted alkyl group in which some or all of the hydrogen atoms are substituted with a halogen atom, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms, or A hydrogen-substituted aryl group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group in which part or all of these hydrogen atoms are substituted with a halogen atom, and ring A is derived from a cyclic compound containing a nitrogen atom. Which is a valent substituent, and the nitrogen atom is bonded to iridium and may have the same substituent as the group defined by X 1 to X 7. Represents a monovalent anionic bidentate ligand having a polymerizable functional group.
［２］ 上記一般式（１）〜（６）において、環Ａが、ピリジン、キノリン、ベンゾオキサゾール、ベンゾチアゾール、ベンゾイミダゾール、ベンゾトリアゾール、イミダゾール、ピラゾール、オキサゾール、チアゾール、トリアゾール、ベンゾピラゾールおよびトリアジンからなる群から選ばれる一種から誘導される２価の置換基であり、該置換基がＸ1〜Ｘ7で定義される基と同様の置換基を有していてもよいことを特徴とする上記［１］に記載の高分子発光材料。 [2] In the general formulas (1) to (6), ring A is selected from pyridine, quinoline, benzoxazole, benzothiazole, benzimidazole, benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazole and triazine. A divalent substituent derived from one selected from the group consisting of the above, wherein the substituent may have the same substituent as the group defined by X 1 to X 7 The polymer light-emitting material according to [1].
［３］ 上記一般式（１）〜（６）におけるＸ1〜Ｘ7、および、環Ａが有する、Ｘ1〜
Ｘ7で定義される基と同様の置換基の少なくとも１つが、フッ素原子またはトリフルオロ
メチル基であることを特徴とする上記［１］または［２］に記載の高分子発光材料。
[3] X 1 ~X 7 in the general formula (1) to (6), and has the ring A, X 1 -
The polymer light-emitting material according to the above [1] or [2], wherein at least one of the substituents similar to the group defined by X 7 is a fluorine atom or a trifluoromethyl group.
［４］ 前記Ｌが、下記一般式（７）〜（１２）のいずれかで表される２座配位子であることを特徴とする上記［１］〜［３］のいずれかに記載の高分子発光材料。 [4] The above-mentioned [1] to [3], wherein L is a bidentate ligand represented by any of the following general formulas (7) to (12) Polymer light emitting material.
（式中、Ｘ1〜Ｘ7はそれぞれ独立に水素原子、ハロゲン原子、シアノ基、ニトロ基、炭素数１〜１０のアルコキシ基、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アルキル基、炭素数６〜２１個のアリール基、炭素数２〜２０のヘテロアリール基もしくは炭素数７〜２１のアラルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アリール基、ハロゲン置換ヘテロアリール基もしくはハロゲン置換アラルキル基を表す。また、環Ａは窒素原子を含む環状化合物から誘導される２価の置換基であり、該窒素原子はイリジウムに結合しており、Ｘ1〜Ｘ7で定義される基と同様の置換基を有していてもよい。但し、Ｘ1〜Ｘ7、および環Ａの有する置換基のうち少なくとも一つは重合性官能基を有する置換基を表す。） (Wherein, X 1 to X 7 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 10 carbon atoms, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or A halogen-substituted alkyl group in which some or all of the hydrogen atoms are substituted with a halogen atom, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an aralkyl group having 7 to 21 carbon atoms, or A hydrogen-substituted aryl group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group in which part or all of these hydrogen atoms are substituted with a halogen atom, and ring A is derived from a cyclic compound containing a nitrogen atom. The nitrogen atom is bonded to iridium and may have the same substituent as the group defined by X 1 to X 7 . And at least one of the substituents of X 1 to X 7 and ring A represents a substituent having a polymerizable functional group.)
［５］ 上記Ｌが、下記一般式（１３）または（１４）で表される２座配位子であることを特徴とする上記［１］〜［３］のいずれかに記載の高分子発光材料。 [5] The polymer luminescence according to any one of [1] to [3], wherein L is a bidentate ligand represented by the following general formula (13) or (14): material.
（式中、Ｘ8は、上記式（１）中のＸ1と同義であり、Ｙ1およびＹ2はそれぞれ独立に、重合性官能基を有する置換基を表す。） (In the formula, X 8 has the same meaning as X 1 in the above formula (1), and Y 1 and Y 2 each independently represent a substituent having a polymerizable functional group.)
［６］ 上記重合体が、さらに、ホール輸送性の重合性化合物および電子輸送性の重合性化合物からなる群より選ばれる少なくとも１種の重合性化合物から導かれる構造単位を含むことを特徴とする上記［１］〜［５］のいずれかに記載の高分子発光材料。 [6] The polymer further includes a structural unit derived from at least one polymerizable compound selected from the group consisting of a hole-transporting polymerizable compound and an electron-transporting polymerizable compound. The polymer light-emitting material according to any one of [1] to [5].
［７］ 陽極と陰極とに挟まれた１層または２層以上の有機高分子層を含む有機エレクトロルミネッセンス素子において、前記有機高分子層の少なくとも１層に、上記［１］〜［６］のいずれかに記載の高分子発光材料を含むことを特徴とする有機エレクトロルミネッセンス素子。 [7] In an organic electroluminescence device including one or more organic polymer layers sandwiched between an anode and a cathode, at least one of the organic polymer layers may include the above-mentioned [1] to [6]. An organic electroluminescence device comprising the polymer light-emitting material according to any one of the above.
［８］ 上記［７］に記載の有機エレクトロルミネッセンス素子を用いた画像表示装置。 [8] An image display device using the organic electroluminescence element according to [7].
［９］ 上記［７］に記載の有機エレクトロルミネッセンス素子を用いた面発光光源。 [9] A surface-emitting light source using the organic electroluminescence device according to [7].
本発明によれば、高い純度の青色光が高い発光効率で得られる高分子発光材料を提供することができる。中でも、発光色の短波長化に有効である。また、本発明によれば、製造工程が簡略化され、大面積化が実現できるとともに、耐久性に優れた有機ＥＬ素子および表示装置を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the polymer light-emitting material from which high purity blue light is obtained with high luminous efficiency can be provided. Among these, it is effective for shortening the wavelength of the emitted color. In addition, according to the present invention, it is possible to provide an organic EL element and a display device that are simplified in manufacturing process, can be increased in area, and are excellent in durability.
有機ＥＬ素子において、青色のりん光発光を得るためには、最低励起状態のエネルギーレベルが高いことが重要である。しかしながら、これまでの金属配位化合物ではその最低励起状態のエネルギーレベルが青色発光するためには低かったため、発光色が青緑色から
赤色になっていたと考えられる。
In an organic EL element, in order to obtain blue phosphorescence, it is important that the energy level of the lowest excited state is high. However, in the conventional metal coordination compounds, the energy level in the lowest excited state was low for blue light emission, and thus the emission color was considered to have changed from blue-green to red.
そこで、本発明者らは種々の検討を行い、上記式（１）〜（６）の何れかで表されるイリジウム錯体から導かれる構造単位を含む重合体からなることを特徴とする高分子発光材料が有効であることを見出した。 Accordingly, the present inventors have made various studies and made a polymer light emission comprising a polymer containing a structural unit derived from an iridium complex represented by any one of the above formulas (1) to (6). We have found that the material is effective.
以下、本発明について具体的に説明する。
本発明に係る高分子発光材料は、特定のイリジウム錯体から導かれる構造単位を含む重合体からなる。このような材料では、イリジウム錯体の三重項励起状態からの発光が得られる。上記高分子発光材料は、さらに、ホール輸送性の重合性化合物および電子輸送性の重合性化合物からなる群から選択される少なくとも１種の重合性化合物から導かれる構造単位を含む重合体からなることが好ましい。
Hereinafter, the present invention will be specifically described.
The polymer light-emitting material according to the present invention comprises a polymer containing a structural unit derived from a specific iridium complex. With such a material, light emission from the triplet excited state of the iridium complex can be obtained. The polymer light emitting material further comprises a polymer including a structural unit derived from at least one polymerizable compound selected from the group consisting of a hole transport polymerizable compound and an electron transport polymerizable compound. Is preferred.
＜イリジウム錯体から導かれる構造単位を含む重合体＞
本発明に用いられる重合体は、上記式（１）〜（６）のいずれかで表されるイリジウム錯体を含む単量体を重合して得られる。上記重合体において、上記イリジウム錯体の単量体は、１種単独で、または２種以上を組み合わせて用いてもよい。本明細書において、上記重合体には、上記錯体の単独重合体、および２種以上の該錯体の共重合体も含む。
<Polymer containing structural unit derived from iridium complex>
The polymer used in the present invention is obtained by polymerizing a monomer containing an iridium complex represented by any of the above formulas (1) to (6). In the said polymer, you may use the monomer of the said iridium complex individually by 1 type or in combination of 2 or more types. In the present specification, the polymer includes a homopolymer of the complex and a copolymer of two or more of the complexes.
上記式（１）〜（６）で表されるイリジウム錯体から導かれる構造単位を含む重合体からなることを特徴とする高分子発光材料は、特定のカルバゾール構造を有する配位子が配位している。そのため、該錯体から導かれる高分子発光材料は青色光を発光する。また、この高分子発光材料によれば、優れた耐久性を有する有機ＥＬ素子を製造できる。 A polymer light-emitting material comprising a polymer containing a structural unit derived from an iridium complex represented by the above formulas (1) to (6) is coordinated by a ligand having a specific carbazole structure. ing. Therefore, the polymer light-emitting material derived from the complex emits blue light. Moreover, according to this polymer light emitting material, an organic EL device having excellent durability can be produced.
上記式（１）〜（６）において、Ｘ1〜Ｘ7はそれぞれ独立に水素原子、ハロゲン原子、シアノ基、ニトロ基、炭素数１〜１０のアルコキシ基、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アルキル基、炭素数６〜２１個のアリール基、炭素数２〜２０のヘテロアリール基もしくは炭素数７〜２１のアラルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アリール基、ハロゲン置換ヘテロアリール基もしくはハロゲン置換アラルキル基を表す。また、環Ａは窒素原子を含む環状化合物から誘導される２価の置換基であり、該窒素原子はイリジウムに結合しており、Ｘ1〜Ｘ7で定義される基と同様の置換基を有していてもよい。 In the above formulas (1) to (6), X 1 to X 7 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxy group having 1 to 10 carbon atoms, or a straight chain having 1 to 22 carbon atoms. , A cyclic or branched alkyl group, or a halogen-substituted alkyl group in which part or all of hydrogen atoms thereof are substituted with a halogen atom, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or a carbon number It represents a halogen-substituted aryl group, a halogen-substituted heteroaryl group or a halogen-substituted aralkyl group in which 7 to 21 aralkyl groups or a part or all of hydrogen atoms thereof are substituted with halogen atoms. Ring A is a divalent substituent derived from a cyclic compound containing a nitrogen atom, and the nitrogen atom is bonded to iridium and has the same substituent as the group defined by X 1 to X 7. You may have.
以下にＸ1〜Ｘ7で表される置換基の例を示すが、本発明においては、以下に限定されるものではない。
Ｘ1〜Ｘ7の例としては、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、シアノ基、ニトロ基、メチル基、エチル基、プロピル基、イソプロピル基、シクロプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、シクロブチル基、ペンチル基、イソペンチル基、ネオペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、シクロヘプチル基、オクチル基、ノニル基、デシル基、フェニル基、トリル基、キシリル基、メシチル基、クメニル基、ベンジル基、フェネチル基、メチルベンジル基、ジフェニルメチル基、スチリル基、シンナミル基、ビフェニル残基、ターフェニル残基、ナフチル基、アントリル基、フルオレニル基、フラン残基、チオフェン残基、ピロール残基、オキサゾール残基、チアゾール残基、イミダゾール残基、ピリジン残基、ピリミジン残基、ピラジン残基、トリアジン残基、キノリン残基、キノキサリン残基またはこれらがフッ素原子、塩素原子、臭素原子、ヨウ素原子等で置換されたハロゲン置換体を挙げることができる。
Show examples of the substituent represented by X 1 to X 7 below, the invention is not limited to the following.
Examples of X 1 to X 7 include hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms and other halogen atoms, cyano groups, nitro groups, methyl groups, ethyl groups, propyl groups, isopropyl groups, and cyclopropyl groups. Butyl group, isobutyl group, tert-butyl group, cyclobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, nonyl group, decyl group, phenyl Group, tolyl group, xylyl group, mesityl group, cumenyl group, benzyl group, phenethyl group, methylbenzyl group, diphenylmethyl group, styryl group, cinnamyl group, biphenyl residue, terphenyl residue, naphthyl group, anthryl group, fluorenyl Group, furan residue, thiophene residue, pyrrole residue, oxa Residue, thiazole residue, imidazole residue, pyridine residue, pyrimidine residue, pyrazine residue, triazine residue, quinoline residue, quinoxaline residue or these are fluorine atom, chlorine atom, bromine atom, iodine atom And the like.
上記式（１）〜（６）で示されるイリジウム錯体のうち、環Ａが、以下に示す構造を有
する環状化合物のいずれかから誘導される２価の置換基であることが好ましい。環Ａが、ピリジン、キノリン、ベンゾオキサゾール、ベンゾチアゾール、ベンゾイミダゾール、ベンゾトリアゾール、イミダゾール、ピラゾール、オキサゾール、チアゾール、トリアゾール、ベンゾピラゾールまたはトリアジンから誘導される２価の置換基（該置換基が、Ｘ1
〜Ｘ7（以下、まとめて「置換基Ｘｎ」とも表記する。）で定義される基と同様の置換基
を有していてもよい。）であることが好ましく、ピリジン、キノリンから誘導される２価の置換基（該置換基が、Ｘｎで定義される基と同様の置換基を有していてもよい。）であることがより好ましい。
Of the iridium complexes represented by the above formulas (1) to (6), the ring A is preferably a divalent substituent derived from any of the cyclic compounds having the structure shown below. Ring A is a divalent substituent derived from pyridine, quinoline, benzoxazole, benzothiazole, benzimidazole, benzotriazole, imidazole, pyrazole, oxazole, thiazole, triazole, benzopyrazole or triazine (the substituent is X 1
To X 7 (hereinafter collectively referred to as "substituent Xn".) May have the same substituent groups as defined in. It is preferably a divalent substituent derived from pyridine or quinoline (which may have the same substituent as the group defined by Xn). preferable.
（ここで、Ｚ1〜Ｚ6は水素原子、ハロゲン原子、シアノ基、ニトロ基、炭素数１〜２２個の直鎖、環状もしくは分岐アルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アルキル基、炭素数６〜２１個のアリール基、炭素数２〜２０のヘテロアリール基もしくは炭素数７〜２１のアラルキル基又はそれらの水素原子の一部もしくは全部がハロゲン原子で置換されたハロゲン置換アリール基、ハロゲン置換
ヘテロアリール基もしくはハロゲン置換アラルキル基であり、また、Ｚ1〜Ｚ6は同一であっても異なっていても良い。）
(Wherein Z 1 to Z 6 are a hydrogen atom, a halogen atom, a cyano group, a nitro group, a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms, or a part or all of these hydrogen atoms are halogen atoms. A halogen-substituted alkyl group, an aryl group having 6 to 21 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, or a part or all of hydrogen atoms thereof is a halogen atom And a halogen-substituted aryl group, a halogen-substituted heteroaryl group, or a halogen-substituted aralkyl group substituted with each other, and Z 1 to Z 6 may be the same or different.
上記式（１）〜（６）で示されるイリジウム錯体において、置換基Ｘｎ、および、環Ａが有する、Ｘｎで定義される基と同様の置換基の少なくとも１つが、発光波長の短波長化に有効であるという観点から、ハロゲン原子、シアノ基またはハロゲン置換アルキル基であることが好ましい。中でも、フッ素原子、塩素原子、シアノ基またはトリフルオロメチル基であることがより好ましく、フッ素原子またはトリフルオロメチル基であることがさらに好ましく、フッ素原子であることが最も好ましい。 In the iridium complex represented by the above formulas (1) to (6), at least one of the substituent Xn and the substituent defined by Xn in the ring A has a shorter emission wavelength. From the viewpoint of effectiveness, a halogen atom, a cyano group, or a halogen-substituted alkyl group is preferable. Among these, a fluorine atom, a chlorine atom, a cyano group, or a trifluoromethyl group is more preferable, a fluorine atom or a trifluoromethyl group is more preferable, and a fluorine atom is most preferable.
置換基Ｘｎ、および、環Ａが有する、Ｘｎで定義される基と同様の置換基の少なくとも１つが、上記いずれかの置換基を有する場合、他のＸｎは水素原子である場合が多いが、さらに他の置換基であってもよい。例えば、Ｘ7はアルキル基またはハロゲン置換アルキ
ル基であることが好ましい。
When at least one of the substituent Xn and the substituent defined by Xn in the ring A has any of the above-mentioned substituents, the other Xn is often a hydrogen atom. Still other substituents may be used. For example, X 7 is preferably an alkyl group or a halogen-substituted alkyl group.
上記式（１）〜（６）で示されるイリジウム錯体中、合成が容易であるという観点から、上記式（１）、（４）で示される金属配位化合物が好ましい。
上記式（１）〜（６）において、Ｌは、重合性官能基を有する、１価アニオンの２座配位子を表す。
Of the iridium complexes represented by the above formulas (1) to (6), the metal coordination compounds represented by the above formulas (1) and (4) are preferable from the viewpoint of easy synthesis.
In the above formulas (1) to (6), L represents a monovalent anion bidentate ligand having a polymerizable functional group.
１価アニオンの２座配位子としては、例えば、水素イオンが１つ脱離して、２つの配位座を含む共役構造が、全体として１価アニオン性となり得る構造を有する化合物から、水素イオンが１つ脱離し、１価のアニオンとなった化合物；または、分子内にピリジン環、カルボニル基、イミン基等の非イオン性の配位座と、水酸基、カルボキシル基等の水素イオンが１つ脱離して１価のアニオン性配位座になり得る部位とを有する化合物などが挙げられる。 As a bidentate ligand of a monovalent anion, for example, from a compound having a structure in which one hydrogen ion is eliminated and a conjugated structure containing two coordination sites can be monovalent anionic as a whole, a hydrogen ion 1 is a monovalent anion; or a nonionic coordination site such as a pyridine ring, a carbonyl group or an imine group and one hydrogen ion such as a hydroxyl group or a carboxyl group in the molecule. And a compound having a moiety that can be desorbed to become a monovalent anionic coordination site.
なお、上記配位子は、重合性官能基を有する置換基以外にも、他の置換基を有していてもよく、該置換基としては、特に制限されず、例えば、Ｘ1で定義される基と同様の置換
基が挙げられる。
The ligand may have other substituents in addition to the substituent having a polymerizable functional group, and the substituent is not particularly limited and is defined by, for example, X 1. And the same substituents as those described above.
Ｌは、重合性官能基を有するが、該官能基は、ラジカル重合性、カチオン重合性、アニオン重合性、付加重合性、および縮合重合性の官能基のいずれであってもよい。これらのうちで、ラジカル重合性の官能基は、重合体の製造が容易であるため好ましい。 L has a polymerizable functional group, and the functional group may be any of radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable, and condensation polymerizable functional groups. Of these, the radical polymerizable functional group is preferable because the production of the polymer is easy.
上記重合性官能基としては、例えば、アリル基、アルケニル基、アクリレート基、メタクリレート基、メタクリロイルオキシエチルカルバメート基等のウレタン（メタ）アクリレート基、ビニルアミド基およびこれらの誘導体などを挙げることができる。これらのうちで、アルケニル基が好ましい。 Examples of the polymerizable functional group include urethane (meth) acrylate groups such as allyl group, alkenyl group, acrylate group, methacrylate group, methacryloyloxyethyl carbamate group, vinylamide group, and derivatives thereof. Of these, alkenyl groups are preferred.
Ｌは、具体的には、上記官能基を、下記一般式（Ａ１）〜（Ａ１２）で表される置換基として有することがより好ましい。これらのうちで、下記式（Ａ１）、（Ａ５）、（Ａ８）、（Ａ１２）で表される置換基は、イリジウム錯体に官能基が容易に導入できるためさらに好ましい。 More specifically, L preferably has the functional group as a substituent represented by the following general formulas (A1) to (A12). Among these, the substituents represented by the following formulas (A1), (A5), (A8), and (A12) are more preferable because functional groups can be easily introduced into the iridium complex.
また、Ｌとしては、上記式（７）〜（１４）のいずれかで表される２座配位子が好ましい。また、より高い発光効率を有し、より長寿命の高分子発光材料が得られるため、上記式（７）〜（１２）で表される２座配位子がより好ましい。 L is preferably a bidentate ligand represented by any of the above formulas (7) to (14). In addition, since a polymer light-emitting material having higher luminous efficiency and a longer lifetime can be obtained, bidentate ligands represented by the above formulas (7) to (12) are more preferable.
上記式（７）〜（１２）において、Ｘ1〜Ｘ7および環Ａはそれぞれ上記式（１）中のＸ1〜Ｘ7および環Ａと同義であるが、Ｘ1〜Ｘ7および環Ａが有する置換基のうち少なくとも
一つは重合性官能基を有する置換基である。
In the above formula (7) ~ (12), X 1 ~X 7 and ring A but are each synonymous with X 1 to X 7 and ring A in the formula (1), X 1 ~X 7 and ring A At least one of the substituents possessed by is a substituent having a polymerizable functional group.
また、上記式（１３）または（１４）においては、Ｘ8は、上記式（１）中のＸ1と同義であり、Ｙ1およびＹ2はそれぞれ独立に、重合性官能基を有する置換基である。
上記式（７）〜（１４）での重合性官能基を有する置換基としては、重合性官能基を有することのほか、特に制限されず、Ｘ1で定義される基と同様の置換基などが挙げられる
。
In the formula (13) or (14), X 8 has the same meaning as X 1 in the formula (1), and Y 1 and Y 2 are each independently a substituent having a polymerizable functional group. It is.
The substituent having a polymerizable functional group in the above formulas (7) to (14) is not particularly limited, other than having a polymerizable functional group, and the same substituent as the group defined by X 1 etc. Is mentioned.
上記重合性官能基としては、上記式（１）〜（６）中のＬにおける重合性官能基と同義であり、好ましい範囲も同じである。具体的には、それぞれ上記式（Ａ１）〜（Ａ１２）で表される置換基であることがより好ましい。これらのうちで、それぞれ上記式（Ａ１）、（Ａ５）、（Ａ８）、（Ａ１２）で表される置換基であることは、イリジウム錯体に官能基が容易に導入できるためさらに好ましい。 As said polymerizable functional group, it is synonymous with the polymerizable functional group in L in said formula (1)-(6), and its preferable range is also the same. Specifically, substituents represented by the above formulas (A1) to (A12) are more preferable. Among these, the substituents represented by the above formulas (A1), (A5), (A8), and (A12) are more preferable because the functional group can be easily introduced into the iridium complex.
上記式（１）で表されるイリジウム錯体は、例えば、以下のように製造することができる。まず、カルバゾール構造を有する配位子と、塩化イリジウムなどのイリジウム化合物（０．５当量）とを、２−エトキシエタノールなどの溶媒中で反応させる。次いで、得られた金属錯体および重合性官能基を有する２座配位子を、炭酸ナトリウムと共に、２−エトキシエタノールなどの溶媒中で加熱した後、精製して、上記式（１）で表されるイリジウム錯体を得る。なお、重合性官能基を有する２座配位子は、公知の方法によって得られる。 The iridium complex represented by the above formula (1) can be produced, for example, as follows. First, a ligand having a carbazole structure is reacted with an iridium compound (0.5 equivalent) such as iridium chloride in a solvent such as 2-ethoxyethanol. Subsequently, the bidentate ligand having a metal complex and a polymerizable functional group obtained was heated in a solvent such as 2-ethoxyethanol together with sodium carbonate, and then purified, and represented by the above formula (1). To obtain an iridium complex. The bidentate ligand having a polymerizable functional group can be obtained by a known method.
また、上記重合体の重量平均分子量は、１，０００〜２，０００，０００であることが好ましく、５，０００〜１，０００，０００であることがより好ましい。本明細書における分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）法を用いて測定されるポリスチレン換算分子量をいう。上記分子量がこの範囲にあると、重合体が有機溶媒に可溶であり、均一な薄膜を得られるため好ましい。 The weight average molecular weight of the polymer is preferably 1,000 to 2,000,000, and more preferably 5,000 to 1,000,000. The molecular weight in this specification means the polystyrene conversion molecular weight measured using GPC (gel permeation chromatography) method. It is preferable for the molecular weight to be in this range since the polymer is soluble in an organic solvent and a uniform thin film can be obtained.
上記重合体は、ランダム共重合体、ブロック共重合体、および交互共重合体のいずれでもよい。
上記重合体の重合方法は、ラジカル重合、カチオン重合、アニオン重合、および付加重合のいずれでもよいが、ラジカル重合が好ましい。
The polymer may be any of a random copolymer, a block copolymer, and an alternating copolymer.
The polymerization method of the polymer may be any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization, but radical polymerization is preferred.
＜キャリア輸送性の重合性化合物から導かれる構造単位を有する重合体＞
本発明に用いられる重合体は、１種または２種以上の上記イリジウム錯体の単量体と共に、ホール輸送性の重合性化合物および電子輸送性の重合性化合物からなる群より選択される少なくとも１種の重合性化合物を含む単量体を共重合して得られる重合体であることが好ましい。なお、本明細書において、ホール輸送性の重合性化合物および電子輸送性の重合性化合物を併せて、キャリア輸送性の重合性化合物ともいう。
<Polymer having a structural unit derived from a carrier transportable polymerizable compound>
The polymer used in the present invention is at least one selected from the group consisting of a hole transporting polymerizable compound and an electron transporting polymerizable compound together with one or more monomers of the above iridium complex. It is preferable that it is a polymer obtained by copolymerizing the monomer containing this polymeric compound. In the present specification, the hole transport polymerizable compound and the electron transport polymerizable compound are also collectively referred to as a carrier transport polymerizable compound.
すなわち、上記高分子発光材料は、１種または２種以上の上記イリジウム錯体から導かれる構造単位と共に、１種または２種以上のホール輸送性の重合性化合物から導かれる構造単位、または１種または２種以上の電子輸送性の重合性化合物から導かれる構造単位をを含む重合体からなることが好ましい。このような高分子発光材料では、上記イリジウム錯体から導かれる構造単位上で、ホールと電子とが効率よく再結合するため、高い発光効率が得られる。 That is, the polymer light-emitting material includes a structural unit derived from one or more hole transportable polymerizable compounds together with a structural unit derived from one or more iridium complexes, or one or more It is preferably made of a polymer containing a structural unit derived from two or more kinds of electron-transporting polymerizable compounds. In such a polymer light-emitting material, holes and electrons are efficiently recombined on the structural unit derived from the iridium complex, so that high luminous efficiency can be obtained.
また、上記高分子発光材料は、１種または２種以上の上記イリジウム錯体から導かれる構造単位と共に、１種または２種以上のホール輸送性の重合性化合物から導かれる構造単位と、１種または２種以上の電子輸送性の重合性化合物から導かれる構造単位とを含む重
合体からなることがより好ましい。このような高分子発光材料は、発光性、ホール輸送性および電子輸送性のすべての機能を備えているため、イリジウム錯体上で、ホールと電子とがさらに効率よく再結合するため、より高い発光効率が得られる。
In addition, the polymer light-emitting material includes a structural unit derived from one or more hole transportable polymerizable compounds together with a structural unit derived from one or more iridium complexes, and one or more structural units. More preferably, it comprises a polymer containing a structural unit derived from two or more kinds of electron-transporting polymerizable compounds. Such a polymer light-emitting material has all the functions of light-emitting property, hole-transporting property, and electron-transporting property, so that holes and electrons recombine more efficiently on the iridium complex, resulting in higher light emission. Efficiency is obtained.
上記ホール輸送性の重合性化合物および上記電子輸送性の重合性化合物は、重合性官能基を有することのほか、特に制限されず、公知のキャリア輸送性の化合物が用いられる。
上記重合性官能基は、ラジカル重合性、カチオン重合性、アニオン重合性、付加重合性、および縮合重合性の官能基のいずれであってもよい。これらのうちで、ラジカル重合性の官能基は、重合体の製造が容易であるため好ましい。
The hole-transporting polymerizable compound and the electron-transporting polymerizable compound are not particularly limited in addition to having a polymerizable functional group, and known carrier-transporting compounds are used.
The polymerizable functional group may be any of radical polymerizable, cationic polymerizable, anionic polymerizable, addition polymerizable, and condensation polymerizable functional groups. Of these, the radical polymerizable functional group is preferable because the production of the polymer is easy.
上記重合性官能基としては、上記式（１）〜（６）中のＬにおける、重合性官能基と同義であり、好ましい範囲も同じである。
上記重合性化合物は、具体的には、上記官能基を、上記式（Ａ１）〜（Ａ１２）で表される置換基として有することがより好ましい。
As said polymerizable functional group, it is synonymous with the polymerizable functional group in L in said Formula (1)-(6), and its preferable range is also the same.
More specifically, the polymerizable compound more preferably has the functional group as a substituent represented by the formulas (A1) to (A12).
上記ホール輸送性の重合性化合物としては、具体的には、下記一般式（Ｅ１）〜（Ｅ６）で表される化合物が好ましく、共重合体におけるキャリア移動度が高いため、下記式（Ｅ１）〜（Ｅ３）で表される化合物がより好ましい。 As the hole transport polymerizable compound, specifically, compounds represented by the following general formulas (E1) to (E6) are preferable, and since the carrier mobility in the copolymer is high, the following formula (E1) The compound represented by (E3) is more preferable.
上記電子輸送性の重合性化合物としては、具体的には、下記一般式（Ｅ７）〜（Ｅ１５）で表される化合物が好ましく、共重合体におけるキャリア移動度が高いため、下記式（Ｅ７）、（Ｅ１２）〜（Ｅ１４）で表される化合物がより好ましい。 Specifically, as the electron transport polymerizable compound, compounds represented by the following general formulas (E7) to (E15) are preferable, and since the carrier mobility in the copolymer is high, the following formula (E7) The compounds represented by (E12) to (E14) are more preferred.
なお、上記式（Ｅ１）〜（Ｅ１５）において、上記式（Ａ１）で表される置換基を、上記一般式（Ａ２）〜（Ａ１２）で表される置換基に代えた化合物も好適に用いられるが、重合性化合物に官能基を容易に導入できるため、上記式（Ａ１）、（Ａ５）で表される置換基を有する化合物が特に好ましい。 In the above formulas (E1) to (E15), a compound in which the substituent represented by the above formula (A1) is replaced with the substituent represented by the above general formula (A2) to (A12) is also preferably used. However, since a functional group can be easily introduced into the polymerizable compound, compounds having substituents represented by the above formulas (A1) and (A5) are particularly preferable.
これらのうちで、上記ホール輸送性の重合性化合物として、上記式（Ｅ１）〜（Ｅ３）のいずれかで表される化合物と、上記電子輸送性の重合性化合物として、上記式（Ｅ７）、（Ｅ１２）〜（Ｅ１４）のいずれかで表される化合物とを、上記イリジウム錯体と組み合わせて共重合させることがより好ましい。このような高分子発光材料は、高い発光効率
および高い最高到達輝度を有し、耐久性にも優れる。この場合に、上記イリジウム錯体として、より長寿命化が図れるため上記式（１）、（４）で表される錯体を用いることが特に好ましい。
Among these, as the hole transport polymerizable compound, the compound represented by any one of the above formulas (E1) to (E3), and as the electron transport polymerizable compound, the above formula (E7), More preferably, the compound represented by any one of (E12) to (E14) is copolymerized in combination with the iridium complex. Such a polymer light emitting material has high luminous efficiency, high maximum luminance, and excellent durability. In this case, as the iridium complex, it is particularly preferable to use a complex represented by the above formulas (1) and (4) because the lifetime can be further increased.
上記式（Ｅ１）〜（Ｅ１５）で表される重合性化合物は、公知の方法によって製造することができる。
なお、上記重合体は、さらに、他の重合性化合物から導かれる構造単位を有していてもよい。上記他の重合性化合物としては、例えば、アクリル酸メチル、メタクリル酸メチル等の（メタ）アクリル酸アルキルエステル、スチレンおよびその誘導体などのキャリア輸送性を有さない化合物が挙げられるが、何らこれらに制限されるものではない。
The polymerizable compound represented by the above formulas (E1) to (E15) can be produced by a known method.
The polymer may further have a structural unit derived from another polymerizable compound. Examples of the other polymerizable compounds include compounds having no carrier transport properties such as (meth) acrylic acid alkyl esters such as methyl acrylate and methyl methacrylate, and styrene and derivatives thereof. It is not limited.
また、上記重合体の重量平均分子量は、１，０００〜２，０００，０００であることが好ましく、５，０００〜１，０００，０００であることがより好ましい。上記分子量がこの範囲にあると、重合体が有機溶媒に可溶であり、均一な薄膜を得られるため好ましい。 The weight average molecular weight of the polymer is preferably 1,000 to 2,000,000, and more preferably 5,000 to 1,000,000. It is preferable for the molecular weight to be in this range since the polymer is soluble in an organic solvent and a uniform thin film can be obtained.
イリジウム錯体と、キャリア輸送性の重合性化合物（ホール輸送性および／または電子輸送性の重合性化合物）との比率を適宜設定すれば、所望の上記重合体が得られ、該重合体は、ランダム共重合体、ブロック共重合体、および交互共重合体のいずれでもよい。 If the ratio of the iridium complex and the carrier-transporting polymerizable compound (hole-transporting and / or electron-transporting polymerizable compound) is appropriately set, the desired polymer can be obtained. Any of a copolymer, a block copolymer, and an alternating copolymer may be sufficient.
上記重合体における、上記イリジウム錯体から導かれる構造単位数をｍとし、キャリア輸送性化合物から導かれる構造単位数（ホール輸送性の重合性化合物および／または電子輸送性の重合性化合物から導かれる構造単位の総数）をｎとしたとき（ｍ、ｎは１以上の整数を示す）、全構造単位数に対する上記イリジウム錯体から導かれる構造単位数の割合、すなわちｍ／（ｍ＋ｎ）の値は、０．００１〜０．５の範囲にあることが好ましく、０．００１〜０．２の範囲にあることがより好ましい。ｍ／（ｍ＋ｎ）の値がこの範囲にあると、キャリア移動度が高く、濃度消光の影響が小さい、高い発光効率の有機ＥＬ素子が得られる。 The number of structural units derived from the iridium complex in the polymer is m, and the number of structural units derived from a carrier transporting compound (a structure derived from a hole transporting polymerizable compound and / or an electron transporting polymerizable compound). When the total number of units is n (m, n represents an integer of 1 or more), the ratio of the number of structural units derived from the iridium complex to the total number of structural units, that is, the value of m / (m + n) is 0. It is preferably in the range of 0.001 to 0.5, and more preferably in the range of 0.001 to 0.2. When the value of m / (m + n) is in this range, an organic EL element having high luminous efficiency with high carrier mobility and low influence of concentration quenching can be obtained.
また、上記重合体が、ホール輸送性化合物から導かれる構造単位と電子輸送性化合物から導かれる構造単位とを含む場合、ホール輸送性化合物から導かれる構造単位数をｘ、電子輸送性化合物から導かれる構造単位数をｙとすると（ｘ、ｙは１以上の整数を示す）、上記ｎとの間に、ｎ＝ｘ＋ｙの関係が成り立つ。キャリア輸送性化合物から導かれる構造単位数に対する、ホール輸送性化合物から導かれる構造単位数の割合ｘ／ｎ、および電子輸送性化合物から導かれる構造単位数の割合ｙ／ｎの最適値は、各構造単位の電荷輸送能、イリジウム錯体から導かれる構造単位の電荷輸送性、濃度などによって決まる。この重合体を有機ＥＬ素子の発光層を形成する唯一の化合物として用いる場合、ｘ／ｎおよびｙ／ｎの値は、それぞれ０．０５〜０．９５の範囲にあることが好ましく、０．２０〜０．８０の範囲にあることがより好ましい。なお、ここで、ｘ／ｎ＋ｙ／ｎ＝１が成り立つ。 In addition, when the polymer includes a structural unit derived from a hole transporting compound and a structural unit derived from an electron transporting compound, the number of structural units derived from the hole transporting compound is derived from x and the electron transporting compound. Assuming that the number of structural units is y (x and y are integers of 1 or more), a relationship of n = x + y is established between n and the above. Optimum values of the ratio x / n of the number of structural units derived from the hole transporting compound and the ratio y / n of the number of structural units derived from the electron transporting compound to the number of structural units derived from the carrier transporting compound are as follows. It depends on the charge transport ability of the structural unit, the charge transportability of the structural unit derived from the iridium complex, the concentration, and the like. When this polymer is used as the only compound for forming the light emitting layer of the organic EL device, the values of x / n and y / n are preferably in the range of 0.05 to 0.95, and 0.20 More preferably in the range of ~ 0.80. Here, x / n + y / n = 1 holds.
上記重合体の重合方法は、ラジカル重合、カチオン重合、アニオン重合、および付加重合のいずれでもよいが、ラジカル重合が好ましい。 The polymerization method of the polymer may be any of radical polymerization, cationic polymerization, anionic polymerization, and addition polymerization, but radical polymerization is preferred.
２．有機エレクトロルミネッセンス素子
本発明に係る高分子発光材料は、有機ＥＬ素子の材料として好適に用いられる。上記有機ＥＬ素子は、陽極と陰極とに挟まれた１層または２層以上の有機高分子層を含み、該有機高分子層の少なくとも１層に、上記高分子発光材料が含まれる。本発明に係る高分子発光材料は、簡便な塗布法で発光層を成膜でき、素子の大面積化が図れる。
2. Organic electroluminescent element The polymer light-emitting material according to the present invention is suitably used as a material for an organic EL element. The organic EL element includes one or more organic polymer layers sandwiched between an anode and a cathode, and at least one of the organic polymer layers includes the polymer light emitting material. With the polymer light emitting material according to the present invention, a light emitting layer can be formed by a simple coating method, and the area of the device can be increased.
本発明に係る有機ＥＬ素子の構成の一例を図１に示すが、本発明に係る有機ＥＬ素子の構成は、これに制限されない。図１では、透明基板（１）上に設けた陽極（２）および陰
極（６）の間に、ホール輸送層（３）、発光層（４）および電子輸送層（５）を、この順で設けている。上記有機ＥＬ素子では、例えば、陽極（２）と陰極（６）の間に、１）ホール輸送層／発光層、２）発光層／電子輸送層のいずれかを設けてもよい。また、３）ホール輸送材料、発光材料、電子輸送材料を含む層、４）ホール輸送材料、発光材料を含む層、５）発光材料、電子輸送材料を含む層、６）発光材料の単独層のいずれかの層を１層のみ設けてもよい。さらに、発光層を２層以上積層してもよい。
An example of the configuration of the organic EL element according to the present invention is shown in FIG. 1, but the configuration of the organic EL element according to the present invention is not limited thereto. In FIG. 1, a hole transport layer (3), a light emitting layer (4) and an electron transport layer (5) are arranged in this order between an anode (2) and a cathode (6) provided on a transparent substrate (1). Provided. In the organic EL device, for example, either 1) a hole transport layer / light emitting layer or 2) a light emitting layer / electron transport layer may be provided between the anode (2) and the cathode (6). In addition, 3) a layer containing a hole transport material, a light emitting material, an electron transport material, 4) a layer containing a hole transport material, a light emitting material, 5) a layer containing a light emitting material, an electron transport material, 6) a single layer of the light emitting material Any one of the layers may be provided. Further, two or more light emitting layers may be stacked.
上記のような素子において、本発明に係る高分子発光材料が、上記イリジウム錯体から導かれる構造単位と、ホール輸送性の重合性化合物から導かれる構造単位と、電子輸送性の重合性化合物から導かれる構造単位とを含む重合体からなる場合は、該材料を含む上記有機高分子層は、ホール輸送性および電子輸送性を併せ持つ発光層として利用できる。このため、他の有機材料の層を設けない場合であっても、高い発光効率および耐久性を有する有機ＥＬ素子を作製できる。また、製造工程がさらに簡略化できる。 In the element as described above, the polymer light-emitting material according to the present invention is derived from a structural unit derived from the iridium complex, a structural unit derived from a hole-transporting polymerizable compound, and an electron-transporting polymerizable compound. In the case of a polymer containing a structural unit to be released, the organic polymer layer containing the material can be used as a light emitting layer having both hole transport properties and electron transport properties. For this reason, even if it is a case where the layer of another organic material is not provided, the organic EL element which has high luminous efficiency and durability can be produced. In addition, the manufacturing process can be further simplified.
上記の各層は、バインダとして高分子材料などを混合して、形成してもよい。上記高分子材料としては、例えば、ポリメチルメタクリレート、ポリカーボネート、ポリエステル、ポリスルホン、ポリフェニレンオキサイドなどが挙げられる。 Each of the above layers may be formed by mixing a polymer material or the like as a binder. Examples of the polymer material include polymethyl methacrylate, polycarbonate, polyester, polysulfone, and polyphenylene oxide.
また、上記の各層に用いられる発光材料、ホール輸送材料および電子輸送材料は、それぞれ単独で各層を形成しても、機能の異なる材料を混合して、各層を形成していてもよい。本発明に係る有機ＥＬ素子における発光層においても、本発明に係る高分子発光材料の他に、キャリア輸送性を補う目的で、さらに他のホール輸送材料および／または電子輸送材料が含まれていてもよい。このような輸送材料としては、低分子化合物であっても、高分子化合物であってもよい。 In addition, the light emitting material, the hole transport material, and the electron transport material used for each of the above layers may be formed independently, or may be formed by mixing materials having different functions. In the light emitting layer in the organic EL device according to the present invention, in addition to the polymer light emitting material according to the present invention, other hole transport materials and / or electron transport materials are further included for the purpose of supplementing the carrier transport property. Also good. Such a transport material may be a low molecular compound or a high molecular compound.
上記ホール輸送層を形成するホール輸送材料、または発光層と混合させるホール輸送材料としては、例えば、ＴＰＤ（Ｎ，Ｎ’−ジメチル−Ｎ，Ｎ’−（３−メチルフェニル）−１，１’−ビフェニル−４，４’ジアミン）；α−ＮＰＤ（４，４’−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］ビフェニル）；ｍ−ＭＴＤＡＴＡ（４、４’，４’’−トリス（３−メチルフェニルフェニルアミノ）トリフェニルアミン）等の低分子トリフェニルアミン誘導体；ポリビニルカルバゾール；上記トリフェニルアミン誘導体に重合性官能基を導入して重合した高分子化合物；ポリパラフェニレンビニレン、ポリジアルキルフルオレン等の蛍光発光性高分子化合物などが挙げられる。上記高分子化合物としては、例えば、特開平８−１５７５７５号公報に開示されているトリフェニルアミン骨格の高分子化合物などが挙げられる。上記ホール輸送材料は、１種単独でも、２種以上を混合して用いてもよく、異なるホール輸送材料を積層して用いてもよい。ホール輸送層の厚さは、ホール輸送層の導電率などに依存するが、通常、好ましくは１ｎｍ〜５μｍ、より好ましくは５ｎｍ〜１μｍ、特に好ましくは１０ｎｍ〜５００ｎｍであることが望ましい。 Examples of the hole transport material forming the hole transport layer or the hole transport material mixed with the light emitting layer include TPD (N, N′-dimethyl-N, N ′-(3-methylphenyl) -1,1 ′. -Biphenyl-4,4'diamine); α-NPD (4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl); m-MTDATA (4,4 ', 4' '- Low molecular weight triphenylamine derivatives such as tris (3-methylphenylphenylamino) triphenylamine); polyvinylcarbazole; a polymer compound obtained by polymerizing a triphenylamine derivative by introducing a polymerizable functional group; polyparaphenylene vinylene; Examples thereof include fluorescent light-emitting polymer compounds such as polydialkylfluorene. Examples of the polymer compound include a polymer compound having a triphenylamine skeleton disclosed in JP-A-8-157575. The hole transport materials may be used singly or in combination of two or more, or different hole transport materials may be laminated and used. The thickness of the hole transport layer depends on the conductivity of the hole transport layer, but is usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm.
上記電子輸送層を形成する電子輸送材料、または発光層と混合させる電子輸送材料としては、例えば、Ａｌｑ３（アルミニウムトリスキノリノレート）等のキノリノール誘導体金属錯体、オキサジアゾール誘導体、トリアゾール誘導体、イミダゾール誘導体、トリアジン誘導体、トリアリールボラン誘導体等の低分子化合物；上記の低分子化合物に重合性置換基を導入して重合した高分子化合物を挙げることができる。上記高分子化合物としては、例えば、特開平１０−１６６５号公報に開示されているポリＰＢＤなどが挙げられる。上記電子輸送材料は、１種単独でも、２種以上を混合して用いてもよく、異なる電子輸送材料を積層して用いてもよい。電子輸送層の厚さは、電子輸送層の導電率などに依存するが、通常、好ましくは１ｎｍ〜５μｍ、より好ましくは５ｎｍ〜１μｍ、特に好ましくは１０ｎｍ〜５００ｎｍであることが望ましい。 Examples of the electron transport material forming the electron transport layer or the electron transport material mixed with the light emitting layer include quinolinol derivative metal complexes such as Alq3 (aluminum trisquinolinolate), oxadiazole derivatives, triazole derivatives, and imidazole derivatives. And low molecular compounds such as triazine derivatives and triarylborane derivatives; and polymer compounds obtained by introducing a polymerizable substituent into the above low molecular compounds. Examples of the polymer compound include poly PBD disclosed in JP-A-10-1665. The electron transport materials may be used singly or in combination of two or more, or different electron transport materials may be laminated and used. Although the thickness of the electron transport layer depends on the conductivity of the electron transport layer, etc., it is usually preferably 1 nm to 5 μm, more preferably 5 nm to 1 μm, and particularly preferably 10 nm to 500 nm.
また、発光層の陰極側に隣接して、ホールが発光層を通過することを抑え、発光層内でホールと電子とを効率よく再結合させる目的で、ホール・ブロック層が設けられていてもよい。上記ホール・ブロック層の形成には、トリアゾール誘導体、オキサジアゾール誘導体、フェナントロリン誘導体などの公知の材料が用いられる。 Further, a hole block layer may be provided adjacent to the cathode side of the light emitting layer for the purpose of suppressing holes from passing through the light emitting layer and efficiently recombining holes and electrons in the light emitting layer. Good. For the formation of the hole block layer, a known material such as a triazole derivative, an oxadiazole derivative, or a phenanthroline derivative is used.
陽極とホール輸送層との間、または陽極と陽極に隣接して積層される有機層との間に、ホール注入において注入障壁を緩和するために、バッファ層が設けられていてもよい。上記バッファ層を形成するためには、銅フタロシアニン、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）とポリスチレンスルホン酸（ＰＳＳ）との混合物などの公知の材料が用いられる。 A buffer layer may be provided between the anode and the hole transport layer or between the anode and the organic layer stacked adjacent to the anode in order to relax the injection barrier in hole injection. In order to form the buffer layer, a known material such as copper phthalocyanine, a mixture of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PSS) is used.
陰極と電子輸送層との間、または陰極と陰極に隣接して積層される有機層との間に、電子注入効率を向上するために、厚さ０．１〜１０ｎｍの絶縁層が設けられていてもよい。上記絶縁層を形成するためには、フッ化リチウム、フッ化マグネシウム、酸化マグネシウム、アルミナなどの公知の材料が用いられる。 An insulating layer having a thickness of 0.1 to 10 nm is provided between the cathode and the electron transport layer or between the cathode and the organic layer laminated adjacent to the cathode in order to improve the electron injection efficiency. May be. In order to form the insulating layer, known materials such as lithium fluoride, magnesium fluoride, magnesium oxide, and alumina are used.
本発明に係る有機ＥＬ素子に用いる陽極材料としては、例えば、ＩＴＯ（酸化インジウムスズ）、酸化錫、酸化亜鉛、ポリチオフェン、ポリピロール、ポリアニリン等の導電性高分子など、公知の透明導電材料が好適に用いられる。この透明導電材料によって形成された電極の表面抵抗は、１〜５０Ω／□（オーム／スクエアー）であることが好ましい。陽極の厚さは５０〜３００ｎｍであることが好ましい。 As the anode material used for the organic EL device according to the present invention, for example, a known transparent conductive material such as ITO (indium tin oxide), tin oxide, zinc oxide, polythiophene, polypyrrole, polyaniline or other conductive polymer is preferably used. Used. The surface resistance of the electrode formed of the transparent conductive material is preferably 1 to 50Ω / □ (ohm / square). The thickness of the anode is preferably 50 to 300 nm.
本発明に係る有機ＥＬ素子に用いる陰極材料としては、例えば、Ｌｉ、Ｎａ、Ｋ、Ｃｓ等のアルカリ金属；Ｍｇ、Ｃａ、Ｂａ等のアルカリ土類金属；Ａｌ；ＭｇＡｇ合金；ＡｌＬｉ、ＡｌＣａ等のＡｌとアルカリ金属との合金など、公知の陰極材料が好適に用いられる。陰極の厚さは、好ましくは１０ｎｍ〜１μｍ、より好ましくは５０〜５００ｎｍであることが望ましい。アルカリ金属、アルカリ土類金属などの活性の高い金属を使用する場合には、陰極の厚さは、好ましくは０．１〜１００ｎｍ、より好ましくは０．５〜５０ｎｍであることが望ましい。また、この場合には、上記陰極金属を保護する目的で、この陰極上に、大気に対して安定な金属層が積層される。上記金属層を形成する金属として、例えば、Ａｌ、Ａｇ、Ａｕ、Ｐｔ、Ｃｕ、Ｎｉ、Ｃｒなどが挙げられる。上記金属層の厚さは、好ましくは１０ｎｍ〜１μｍ、より好ましくは５０〜５００ｎｍであることが望ましい。 Examples of the cathode material used in the organic EL device according to the present invention include alkali metals such as Li, Na, K, and Cs; alkaline earth metals such as Mg, Ca, and Ba; Al; MgAg alloys; AlLi, AlCa, and the like. A known cathode material such as an alloy of Al and an alkali metal is preferably used. The thickness of the cathode is preferably 10 nm to 1 μm, more preferably 50 to 500 nm. When a highly active metal such as an alkali metal or alkaline earth metal is used, the thickness of the cathode is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm. In this case, a metal layer that is stable to the atmosphere is laminated on the cathode for the purpose of protecting the cathode metal. Examples of the metal forming the metal layer include Al, Ag, Au, Pt, Cu, Ni, and Cr. The thickness of the metal layer is preferably 10 nm to 1 μm, more preferably 50 to 500 nm.
本発明に係る有機ＥＬ素子の基板としては、上記発光材料の発光波長に対して透明な絶縁性基板が好適に用いられ、具体的には、ガラスのほか、ＰＥＴ（ポリエチレンテレフタレート）、ポリカーボネート等の透明プラスチックなどが用いられる。 As the substrate of the organic EL device according to the present invention, an insulating substrate that is transparent with respect to the emission wavelength of the light emitting material is preferably used. Specifically, in addition to glass, PET (polyethylene terephthalate), polycarbonate, etc. Transparent plastics are used.
上記のホール輸送層、発光層および電子輸送層の成膜方法としては、例えば、抵抗加熱蒸着法、電子ビーム蒸着法、スパッタリング法、インクジェット法、スピンコート法、印刷法、スプレー法、ディスペンサー法などを用いることができる。低分子化合物の場合は、抵抗加熱蒸着または電子ビーム蒸着が好適に用いられ、高分子材料の場合は、インクジェット法、スピンコート法、または印刷法が好適に用いられる。 Examples of the film formation method of the hole transport layer, the light emitting layer, and the electron transport layer include a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, an ink jet method, a spin coating method, a printing method, a spray method, and a dispenser method. Can be used. In the case of a low molecular compound, resistance heating vapor deposition or electron beam vapor deposition is preferably used, and in the case of a polymer material, an ink jet method, a spin coating method, or a printing method is suitably used.
本発明に係る高分子発光材料を用いて発光層を成膜する場合は、インクジェット法、スピンコート法、ディップコート法または印刷法が好ましく用いられるため、製造工程が簡略化され、素子の大面積化も図れる。 In the case of forming a light emitting layer using the polymer light emitting material according to the present invention, an inkjet method, a spin coating method, a dip coating method or a printing method is preferably used, so that the manufacturing process is simplified, and the large area of the device Can also be achieved.
また、上記陽極材料の成膜方法としては、例えば、電子ビーム蒸着法、スパッタリング法、化学反応法、コーティング法などが用いられ、上記陰極材料の成膜方法としては、例
えば、抵抗加熱蒸着法、電子ビーム蒸着法、スパッタリング法、イオンプレーティング法などが用いられる。
In addition, as a method for forming the anode material, for example, an electron beam evaporation method, a sputtering method, a chemical reaction method, a coating method, or the like is used. As a method for forming the cathode material, for example, a resistance heating evaporation method, An electron beam evaporation method, a sputtering method, an ion plating method, or the like is used.
３．用途
本発明に係る有機ＥＬ素子は、公知の方法で、マトリックス方式またはセグメント方式による画素として画像表示装置に好適に用いられる。また、上記有機ＥＬ素子は、画素を形成せずに、面発光光源としても好適に用いられる。
3. Use The organic EL device according to the present invention is suitably used in an image display device as a pixel by a matrix method or a segment method by a known method. The organic EL element is also suitably used as a surface light source without forming pixels.
本発明に係る有機ＥＬ素子は、具体的には、ディスプレイ、バックライト、電子写真、照明光源、記録光源、露光光源、読み取り光源、標識、看板、インテリア、光通信などに好適に用いられる。
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
Specifically, the organic EL device according to the present invention is suitably used for displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
［実施例］
［合成例１］
（１−１）配位子（Ａ）の合成
スキーム１
[Example]
[Synthesis Example 1]
(1-1) Synthesis Scheme 1 of Ligand (A)
３−（２'−ピリジル）−９−メチルカルバゾール（特開２００５−０２３０７０号公
報に記載された方法により合成した。）１．５４ｇ（６．０ｍｍｏｌ）をクロロホルム９０ｍＬに溶解した。この溶液に、塩化アルミニウム１．０ｇ（７．５ｍｍｏｌ）のニトロメタン溶液５ｍＬを加え、室温で５分間撹拌した。得られた反応液に塩化アセチル０．５９ｇ（７．５ｍｍｏｌ）を滴下し、室温で１２時間撹拌した。反応液を水で洗浄後、溶媒を留去し、シリカゲルカラムクロマトグラフィーで精製して、化合物（ａ）を得た。
1.54 g (6.0 mmol) of 3- (2′-pyridyl) -9-methylcarbazole (synthesized by the method described in JP-A-2005-023070) was dissolved in 90 mL of chloroform. To this solution, 5 mL of a nitromethane solution of 1.0 g (7.5 mmol) of aluminum chloride was added and stirred at room temperature for 5 minutes. 0.59 g (7.5 mmol) of acetyl chloride was added dropwise to the resulting reaction solution, and the mixture was stirred at room temperature for 12 hours. The reaction solution was washed with water, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain compound (a).
次いで、化合物（ａ）０．９６ｇ（３．２ｍｍｏｌ）、アルミニウムトリイソプロポキシド０．６６ｇ（３．２ｍｍｏｌ）およびキシレン２０ｍＬの混合物を１．５時間加熱還流した。得られた反応液を水で洗浄後、溶媒を留去し、シリカゲルカラムクロマトグラフィーで精製して、配位子（Ａ）０．６５ｇ（２．３ｍｍｏｌ）を得た（スキーム１）。 Next, a mixture of 0.96 g (3.2 mmol) of compound (a), 0.66 g (3.2 mmol) of aluminum triisopropoxide and 20 mL of xylene was heated to reflux for 1.5 hours. The obtained reaction solution was washed with water, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.65 g (2.3 mmol) of the ligand (A) (Scheme 1).
配位子（Ａ）の同定データは以下の通りである。
元素分析： 計算値(Ｃ20Ｈ16Ｎ2)Ｃ ８４．５１； Ｈ ５．６３； Ｎ ９．８６
実測値 Ｃ ８４．７３； Ｈ ５．４２； Ｎ ９．９９
質量分析(EI)： (M+) ２８４
（１−２）イリジウム錯体（Ｂ）の合成
スキーム２
Identification data of the ligand (A) are as follows.
Calcd (C 20 H 16 N 2) C 84.51; H 5.63; N 9.86
Found C 84.73; H 5.42; N 9.99
Mass spectrometry (EI): (M + ) 284
(1-2) Synthesis scheme 2 of iridium complex (B)
上記スキーム２のように合成した。化合物（ｃ）（特開２００５−０２３０７０号公報に記載された方法により合成した。）０．７６ｇ（０．５１ｍｍｏｌ）と配位子（Ａ）０．２８ｇ（１．０ｍｍｏｌ）との混合物にグリセリン１０ｍＬを加え、１７０℃で４８時間加熱撹拌した。反応液を室温にまで冷却した後、１００ｍＬの水を加え、沈殿を濾取、乾燥した。得られた粗成生物をシリカゲルカラムクロマトグラフィーで精製し、イリジウム錯体（Ｂ）を得た。 Synthesized as in Scheme 2 above. Compound (c) (synthesized by the method described in JP-A-2005-023070). Glycerol was added to a mixture of 0.76 g (0.51 mmol) and ligand (A) 0.28 g (1.0 mmol). 10 mL was added and heated and stirred at 170 ° C. for 48 hours. After cooling the reaction solution to room temperature, 100 mL of water was added, and the precipitate was collected by filtration and dried. The resulting crude product was purified by silica gel column chromatography to obtain an iridium complex (B).
イリジウム錯体（Ｂ）の同定データは以下の通りである。
元素分析： 計算値(Ｃ56Ｈ42ＩｒＮ4)Ｃ ６７．８８； Ｈ ４．２４； Ｎ ８．４
８
実測値 Ｃ ６７．９８； Ｈ ４．３３； Ｎ ８．３５
質量分析(FAB+)： ９９０(M+)
Identification data of the iridium complex (B) is as follows.
Calcd (C 56 H 42 IrN 4) C 67.88; H 4.24; N 8.4
8
Found C 67.98; H 4.33; N 8.35
Mass spectrometry (FAB +): 990 (M + )
［合成例２］イリジウム錯体（Ｄ）の合成
スキーム３
[Synthesis Example 2] Synthesis scheme 3 of iridium complex (D)
上記スキーム３のように合成した。化合物（ｃ）０．５１ｇ（０．３２ｍｍｏｌ）、化合物（ｅ）（特開２００３−１１３２４６号公報に記載の方法に従って合成した。）０．３０ｇ（１．４ｍｍｏｌ）および炭酸ナトリウム０．１５ｇ（１．４ｍｍｏｌ）の混合物に２−エトキシエタノールを加え、１５時間加熱還流した。反応混合物を室温にまで冷却した後、沈殿を濾取し、水、エタノールおよびジエチルエーテルで順に洗浄した。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製し、イリジウム錯体（Ｄ）を得た。 Synthesized as in Scheme 3 above. Compound (c) 0.51 g (0.32 mmol), Compound (e) (synthesized according to the method described in JP-A No. 2003-113246) 0.30 g (1.4 mmol) and sodium carbonate 0.15 g (1 .4 mmol) was added to 2-ethoxyethanol and heated to reflux for 15 hours. After the reaction mixture was cooled to room temperature, the precipitate was collected by filtration and washed in turn with water, ethanol and diethyl ether. The obtained crude product was purified by silica gel column chromatography to obtain an iridium complex (D).
イリジウム錯体（Ｄ）の同定データは以下の通りである。
元素分析： 計算値(Ｃ50Ｈ41ＩｒＮ4Ｏ2)Ｃ ６５．１５； Ｈ ４．４５； Ｎ ６．０８
実測値 Ｃ ６５．２８； Ｈ ４．３３； Ｎ ６．２０
質量分析(FAB+)： ９２１ (M+)
Identification data of the iridium complex (D) is as follows.
Calcd (C 50 H 41 IrN 4 O 2) C 65.15; H 4.45; N 6.08
Found C 65.28; H 4.33; N 6.20
Mass spectrometry (FAB +): 921 (M + )
［実施例１］共重合体（Ｉ）の合成
密閉容器に、イリジウム錯体（Ｂ）８０ｍｇ、上記式（Ｅ１）で表される化合物（特開２００５−９７５８９号公報に記載の方法に従って合成した）４６０ｍｇ、および上記式（Ｅ７）で表される化合物（特開平１０−１６６５号公報に記載の方法に従って合成した
）４６０ｍｇを入れ、脱水トルエン（９．９ｍＬ）を加えた。次いで、Ｖ−６０１（和光純薬工業（株）製）のトルエン溶液（０．１Ｍ、１９８μＬ）を加え、凍結脱気操作を５回繰り返した。真空のまま密閉し、６０℃で６０時間撹拌した。反応後、反応液をアセトン５００ｍＬ中に滴下し、沈殿を得た。さらにトルエン−アセトンでの再沈殿精製を２回繰り返した後、５０℃で一晩真空乾燥して、共重合体（Ｉ）を得た。
[Example 1] Synthesis of copolymer (I) 80 mg of iridium complex (B) in a sealed container, compound represented by the above formula (E1) (synthesized according to the method described in JP-A-2005-97589) 460 mg and 460 mg of a compound represented by the above formula (E7) (synthesized according to the method described in JP-A-10-1665) were added, and dehydrated toluene (9.9 mL) was added. Subsequently, a toluene solution (0.1 M, 198 μL) of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the freeze degassing operation was repeated 5 times. It sealed in vacuum and stirred at 60 ° C. for 60 hours. After the reaction, the reaction solution was dropped into 500 mL of acetone to obtain a precipitate. Further, reprecipitation purification with toluene-acetone was repeated twice, followed by vacuum drying at 50 ° C. overnight to obtain a copolymer (I).
共重合体（Ｉ）の重量平均分子量（Ｍｗ）は７３２００、分子量分布指数（Ｍｗ／Ｍｎ）は１．８３であった。ＩＣＰ元素分析および13Ｃ−ＮＭＲ測定の結果から見積もった共重合体におけるｍ／（ｍ＋ｎ）の値は０．０２９であった。また、共重合体（Ｉ）において、ｘ／ｎの値は、０．４２であり、ｙ／ｎの値は、０．５８であった。 The weight average molecular weight (Mw) of the copolymer (I) was 73200, and the molecular weight distribution index (Mw / Mn) was 1.83. The m / (m + n) value of the copolymer estimated from the results of ICP elemental analysis and 13 C-NMR measurement was 0.029. In copolymer (I), the value of x / n was 0.42, and the value of y / n was 0.58.
［実施例２］共重合体（ＩＩ）の合成
イリジウム錯体（Ｂ）の代わりにイリジウム錯体（Ｄ）を、上記式（Ｅ１）で表される化合物の代わりに上記式（Ｅ２）で表される化合物（特開２００５−２００６３８号公報に記載の方法に従って合成した）を、上記式（Ｅ７）で表される化合物の代わりに上記式（Ｅ１４）で表される化合物（特開２００５−２００６３８号公報に記載の方法に従って合成した）を用いた他は、実施例１と同様にして、共重合体（ＩＩ）を得た。
[Example 2] Synthesis of copolymer (II) The iridium complex (D) is represented by the above formula (E2) instead of the compound represented by the above formula (E1) instead of the iridium complex (B). A compound (synthesized according to the method described in Japanese Patent Application Laid-Open No. 2005-201568) was replaced with a compound represented by the above formula (E14) (Japanese Patent Application Laid-Open No. 2005-006368) instead of the compound represented by the above formula (E7). The copolymer (II) was obtained in the same manner as in Example 1 except that the above compound was synthesized according to the method described in 1).
共重合体（ＩＩ）の重量平均分子量（Ｍｗ）は６６５００、分子量分布指数（Ｍｗ／Ｍｎ）は１．９１であった。ＩＣＰ元素分析および13Ｃ−ＮＭＲ測定の結果から見積もった共重合体におけるｍ／（ｍ＋ｎ）の値は０．０３０であった。また、共重合体（ＩＩ）において、ｘ／ｎの値は、０．４１であり、ｙ／ｎの値は、０．５９であった。 The copolymer (II) had a weight average molecular weight (Mw) of 66500 and a molecular weight distribution index (Mw / Mn) of 1.91. The m / (m + n) value of the copolymer estimated from the results of ICP elemental analysis and 13 C-NMR measurement was 0.030. In copolymer (II), the value of x / n was 0.41, and the value of y / n was 0.59.
［実施例３］有機ＥＬ素子の作製および発光特性の評価
ＩＴＯ付き基板（ニッポ電機（株）製）を用いた。これは、２５ｍｍ角のガラス基板の一方の面に、幅４ｍｍのＩＴＯ（酸化インジウム錫）電極（陽極）が、ストライプ状に２本形成された基板であった。
[Example 3] Preparation of organic EL element and evaluation of light emission characteristics A substrate with ITO (manufactured by Nippon Electric Co., Ltd.) was used. This was a substrate in which two ITO (indium tin oxide) electrodes (anodes) having a width of 4 mm were formed in one stripe on one surface of a 25 mm square glass substrate.
まず、上記ＩＴＯ付き基板上に、ポリ（３，４−エチレンジオキシチオフェン）・ポリスチレンスルホン酸（バイエル（株）製、商品名「バイトロンＰ」）を、回転数３５００ｒｐｍ、塗布時間４０秒の条件で、スピンコート法により塗布した。その後、真空乾燥器で減圧下、６０℃で２時間乾燥し、陽極バッファ層を形成した。得られた陽極バッファ層の膜厚は、約５０ｎｍであった。次に、共重合体（Ｉ）９０ｍｇをトルエン（和光純薬工業（株）製、特級）２９１０ｍｇに溶解し、この溶液を孔径０．２μｍのフィルターでろ過し、塗布溶液を調製した。次いで、上記陽極バッファ層上に、上記塗布溶液を、回転数３０００ｒｐｍ、塗布時間３０秒の条件で、スピンコート法により塗布した。塗布後、室温（２５℃）で３０分間乾燥し、発光層を形成した。得られた発光層の膜厚は、約１００ｎｍであった。 First, poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid (manufactured by Bayer Co., Ltd., trade name “BYTRON P”) on the above-mentioned ITO-attached substrate under conditions of a rotation speed of 3500 rpm and a coating time of 40 seconds. Then, it was applied by spin coating. Then, it dried for 2 hours at 60 degreeC under pressure reduction with the vacuum dryer, and formed the anode buffer layer. The film thickness of the obtained anode buffer layer was about 50 nm. Next, 90 mg of copolymer (I) was dissolved in 2910 mg of toluene (special grade, manufactured by Wako Pure Chemical Industries, Ltd.), and this solution was filtered with a filter having a pore size of 0.2 μm to prepare a coating solution. Next, the coating solution was coated on the anode buffer layer by spin coating under the conditions of a rotation speed of 3000 rpm and a coating time of 30 seconds. After the application, it was dried at room temperature (25 ° C.) for 30 minutes to form a light emitting layer. The film thickness of the obtained light emitting layer was about 100 nm.
次に、発光層を形成した基板を蒸着装置内に載置した。次いで、カルシウムおよびアルミニウムを重量比１：１０で共蒸着し、陽極の延在方向に対して直交するように、幅３ｍｍの陰極をストライプ状に２本形成した。得られた陰極の膜厚は、約５０ｎｍであった。 Next, the substrate on which the light emitting layer was formed was placed in a vapor deposition apparatus. Next, calcium and aluminum were co-evaporated at a weight ratio of 1:10, and two cathodes having a width of 3 mm were formed in a stripe shape so as to be orthogonal to the extending direction of the anode. The film thickness of the obtained cathode was about 50 nm.
最後に、アルゴン雰囲気中で、陽極と陰極とにリード線（配線）を取り付けて、縦４ｍｍ×横３ｍｍの有機ＥＬ素子を４個作製した。上記有機ＥＬ素子に、プログラマブル直流電圧／電流源（ＴＲ６１４３、（株）アドバンテスト社製）を用いて電圧を印加して発光させた。その発光輝度を、輝度計（ＢＭ−８、（株）トプコン社製）を用いて測定した。 Finally, lead wires (wirings) were attached to the anode and the cathode in an argon atmosphere, and four organic EL elements measuring 4 mm in length and 3 mm in width were produced. A voltage was applied to the organic EL element to emit light using a programmable DC voltage / current source (TR6143, manufactured by Advantest Corporation). The emission luminance was measured using a luminance meter (BM-8, manufactured by Topcon Corporation).
作製した有機ＥＬ素子は、青色の発光を示した。青色光は、ＣＩＥ色度座標においてｘ＝０．１５およびｙ＝０．２０であった。最大発光外部量子効率は５．１％、最高輝度は
４６００ｃｄ／ｍ2であった。また初期輝度１００ｃｄ／ｍ2で電流値を一定にして通電して連続発光し、強制劣化させた際、輝度が半減するまで、２０００時間であった。
The produced organic EL element showed blue light emission. Blue light was x = 0.15 and y = 0.20 in CIE chromaticity coordinates. The maximum light emitting external quantum efficiency was 5.1%, and the maximum luminance was 4600 cd / m 2 . In addition, when the current value was kept constant at an initial luminance of 100 cd / m 2 , and the current was continuously emitted by being energized and forcibly deteriorated, it was 2000 hours until the luminance was reduced to half.
［実施例４］有機ＥＬ素子の作製および発光特性の評価
共重合体（Ｉ）の代わりに共重合体（ＩＩ）を用いたほかは、実施例３と同様にして、有機ＥＬ素子を作製し、発光色などの測定を行った。
[Example 4] Production of organic EL device and evaluation of light emission characteristics An organic EL device was produced in the same manner as in Example 3 except that copolymer (II) was used instead of copolymer (I). Measurement of emission color and the like was performed.
作製した有機ＥＬ素子は、青色の発光を示した。得られた青色光は、ＣＩＥ色度座標においてｘ＝０．１５およびｙ＝０．２４であった。最大発光外部量子効率は４．７％、最高輝度は３８００ｃｄ／ｍ2であった。また初期輝度１００ｃｄ／ｍ2で電流値を一定にして通電して連続発光し、強制劣化させた際、輝度が半減するまで、２２００時間であった。 The produced organic EL element showed blue light emission. The resulting blue light was x = 0.15 and y = 0.24 in CIE chromaticity coordinates. The maximum light-emitting external quantum efficiency was 4.7%, and the maximum luminance was 3800 cd / m 2 . In addition, when the current value was kept constant at an initial luminance of 100 cd / m 2 and the device was continuously energized by energization and forced deterioration, it was 2200 hours until the luminance was reduced to half.
１： ガラス基板
２： 陽極
３： ホール輸送層
４： 発光層
５： 電子輸送層
６： 陰極
1: Glass substrate 2: Anode 3: Hole transport layer 4: Light emitting layer 5: Electron transport layer 6: Cathode
Claims (4)
下記一般式（Ｅ１）〜（Ｅ６）のいずれかで表わされるホール輸送性の重合性化合物から導かれる構造単位と、
下記一般式（Ｅ７）〜（Ｅ１５）のいずれかで表わされる電子輸送性の重合性化合物から導かれる構造単位と、
を含む重合体からなることを特徴とする高分子発光材料。
A structural unit derived from a hole transport polymerizable compound represented by any one of the following general formulas (E1) to (E6);
A structural unit derived from an electron-transporting polymerizable compound represented by any one of the following general formulas (E7) to (E15);
A polymer light-emitting material comprising a polymer containing
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005328724A JP4790381B2 (en) | 2005-11-14 | 2005-11-14 | Polymer light-emitting material, organic electroluminescence element, and display device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005328724A JP4790381B2 (en) | 2005-11-14 | 2005-11-14 | Polymer light-emitting material, organic electroluminescence element, and display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007131813A JP2007131813A (en) | 2007-05-31 |
| JP4790381B2 true JP4790381B2 (en) | 2011-10-12 |
Family
ID=38153727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005328724A Active JP4790381B2 (en) | 2005-11-14 | 2005-11-14 | Polymer light-emitting material, organic electroluminescence element, and display device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4790381B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4790382B2 (en) * | 2005-11-14 | 2011-10-12 | 昭和電工株式会社 | Polymer light-emitting material, organic electroluminescence element, and display device |
| JP4916792B2 (en) * | 2006-06-29 | 2012-04-18 | 昭和電工株式会社 | Organic electroluminescence element and display device |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4035976B2 (en) * | 2001-10-02 | 2008-01-23 | 昭和電工株式会社 | Polymerizable compound and method for producing the same |
| JP4574936B2 (en) * | 2001-08-31 | 2010-11-04 | 日本放送協会 | Phosphorescent compound and phosphorescent composition |
| JP3890242B2 (en) * | 2002-03-26 | 2007-03-07 | キヤノン株式会社 | Polymer compound and electroluminescent device |
| JP4380432B2 (en) * | 2003-06-18 | 2009-12-09 | 日立化成工業株式会社 | Polymer copolymer containing metal coordination compound and organic electroluminescence device using the same |
| JP4380433B2 (en) * | 2003-06-18 | 2009-12-09 | 日立化成工業株式会社 | Polymer copolymer containing metal coordination compound and organic electroluminescence device using the same |
| JP4380431B2 (en) * | 2003-06-18 | 2009-12-09 | 日立化成工業株式会社 | Polymer copolymer containing metal coordination compound and organic electroluminescence device using the same |
| JP4854956B2 (en) * | 2003-12-19 | 2012-01-18 | 昭和電工株式会社 | Boron-containing polymer compound and organic light-emitting device using the same |
| JP4790382B2 (en) * | 2005-11-14 | 2011-10-12 | 昭和電工株式会社 | Polymer light-emitting material, organic electroluminescence element, and display device |
-
2005
- 2005-11-14 JP JP2005328724A patent/JP4790381B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007131813A (en) | 2007-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4879591B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP5043329B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP5043330B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP2007031678A (en) | Polymeric luminescent material and organic electroluminescence element using the polymeric luminescent material | |
| JP4964482B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP4896512B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP2007262135A (en) | Polymer luminescent material, organic electroluminescent element and display | |
| JP4916791B2 (en) | Organic electroluminescence element and display device | |
| JP4790382B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP4823601B2 (en) | Polymer light emitting material, organic electroluminescence element, and display device | |
| JP2007254539A (en) | Polymer luminescent material, organoelectroluminescent element and display device | |
| JP4916792B2 (en) | Organic electroluminescence element and display device | |
| JP4749871B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP2007084612A (en) | High molecular light emission material, organic electroluminescent element and display | |
| JP4954581B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP4932238B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP4790381B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP4954582B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP4943029B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP5105782B2 (en) | Organic electroluminescence element and display device | |
| JP4717629B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP4749887B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP5043346B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP4790383B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device | |
| JP4932267B2 (en) | Polymer light-emitting material, organic electroluminescence element, and display device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20081105 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110202 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110208 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110408 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110712 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110720 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140729 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4790381 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |